CN1215308A - 杀菌混合物 - Google Patents
杀菌混合物 Download PDFInfo
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- CN1215308A CN1215308A CN97193717A CN97193717A CN1215308A CN 1215308 A CN1215308 A CN 1215308A CN 97193717 A CN97193717 A CN 97193717A CN 97193717 A CN97193717 A CN 97193717A CN 1215308 A CN1215308 A CN 1215308A
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及包括协同作用量的式(Ⅰ)的肟醚羧酸酯、式(Ⅱ)的肟醚羧酸酰胺以及式(Ⅲ)的吡咯作为活性成分的杀菌混合物。
Description
本发明涉及一种杀菌混合物,它包括协同作用量的一种化学式为Ⅰ的肟醚羧酸酯和一种化学式为Ⅱ的肟醚羧酸酰胺,以及还有一种化学式为Ⅲ的吡咯。
另外,本发明涉及使用化合物Ⅰ,Ⅱ,Ⅲ的混合物控制有害真菌的方法以及化合物Ⅰ,Ⅱ,Ⅲ在制备这种混合物中的用途。
化学式为Ⅰ,Ⅱ的化合物,它们的制备以及它们抗有害真菌的作用在文献中(EP-A 253 213,EP-A 398 692,EP-A 477 631)被公开。
化学式为Ⅲ的化合物,它的制备以及它对作为杀菌剂的用途(建议商品名:Epoxiconazole,EP-A 196 038)也被公开。
为了减少使用比例和提高所知化合物的作用范围,本发明的目的就是基于在使用更少的活性成份的总量情况下对有害真菌具有增强作用力的混合物(协同混合物)。
我们已经发现用开始所定义的混合物可以达到这个目的,而且我们发现同时一起或分开使用化合物Ⅰ,Ⅱ,Ⅲ或连续地使用化合物Ⅰ,Ⅱ,Ⅲ比使用单种化合物可以具有更好的有害真菌控制作用。
关于C=N双键,化学式为Ⅰ,Ⅱ的化合物可以以反式(E)或顺式(Z)构型存在(对于羧酸官能团而言)。因此,任一情况下,它们可以在本发明混合物中以纯E或Z异构体形式或以E/Z异构体混合物形式被使用。优选使用E/Z异构体混合物或E型异构体,尤其优选E型异构体。
当提供混合物时,优选采用纯的活性成份Ⅰ,Ⅱ,Ⅲ,根据需要,它们能够与其它控制有害真菌或其它害虫如昆虫,蜘蛛类节肢动物或线虫的活性成份,或其它除草的或控制生长的活性成份或肥料混合。
化合物Ⅰ,Ⅱ,Ⅲ的混合物,或化合物Ⅰ,Ⅱ,Ⅲ一起使用或分开使用的特征是对广泛范围的植物致病性真菌有极好的作用力,特别是属子囊菌纲,半知菌纲,担子菌纲和藻状菌纲类的真菌。它们有时能够作用整个体系,也能作为叶子杀菌剂和土壤杀菌剂。
它们对控制各种栽培作物如棉花,蔬菜植物(如黄瓜,菜豆属植物,葫芦),大麦,草,燕麦,咖啡,玉米,水果植物,水稻,黑麦,大豆,葡萄,小麦,观赏植物,甘蔗,以及各种各样的种子上的大量真菌有特别重要的意义。
它们特别适合控制下面植物致病性真菌:谷类上的禾白粉菌(粉化霉菌),葫芦上的二孢白粉菌和单丝壳,苹果上的白叉丝单囊壳,谷类上的柄锈菌属,棉花,水稻和草坪上的丝核菌属,谷类和甘蔗上的黑粉菌属,苹果上的苹果黑星菌(黑星病),谷类上的长蠕孢属,小麦上的颖枯壳针孢,草莓,蔬菜,观赏植物和葡萄藤上的灰葡萄孢(灰霉病),花生上的落花生尾孢(花生黑斑病),小麦和黑麦上的Pseudocercosporellaherpotrichoides,水稻上的Pyricularia oryzae,马铃薯和西红柿上的致病疫霉,葡萄藤上的葡萄生单轴霉,蛇麻草和黄瓜上的假霜霉属,蔬菜和水果上的链格孢属以及镰孢霉属和轮枝孢属。
此外,它们能够用于材料的保护(如木材的保护),例如防治拟青霉。
化合物Ⅰ,Ⅱ和Ⅲ可以同时一起或分开或连续地使用,在分开使用的情况下的顺序一般不影响这种控制方法的结果。
使用化合物Ⅰ和Ⅱ一般以重量比1∶0.1至1∶10,优选1∶5至1∶0.2,特别优选1∶3至1∶0.3 (Ⅰ∶Ⅱ)。
使用化合物Ⅰ和Ⅲ一般以重量比1∶0.1至1∶10,优选1∶0.1至1∶5,特别优选1∶0.2至1∶3(Ⅰ∶Ⅲ)。
根据所希望的效果的性质,依据本发明混合物的使用比例为0.003~3.0kg/ha(公斤/公顷),优选0.02~2.0kg/ha,特别优选0.07~1.5kg/ha。
化合物Ⅰ在此的使用比例为0.001~1.0kg/ha,优选0.05~0.5kg/ha,特别优选0.01~0.3kg/ha。
相应化合物Ⅱ的使用比例为0.001~0.1kg/ha,优选0.05~0.5kg/ha,特别优选0.01~0.3kg/ha。
化合物Ⅲ的使用比例为0.001~1.0kg/ha,优选0.05~1.0kg/ha,特别优选0.05~0.5kg/ha。
在处理种子时,混合物使用比例一般为0.001~50g/kg种子,优选0.01~10g/kg,特别优选0.01~5g/kg。
如果是控制植物致病性有害真菌,则化合物Ⅰ,Ⅱ,Ⅲ分开或一起使用或化合物Ⅰ,Ⅱ,Ⅲ的混合物使用是通过在种作物之前或之后,或作物长出之前或之后喷洒或撒粉种子,植物或土壤。
根据本发明,杀菌剂的协同混合物,或化合物Ⅰ,Ⅱ,Ⅲ可以配成如可直接喷射的溶液,粉料和悬浮液的形式或高度浓缩的水溶液,油溶液或其它悬浮液,分散液,乳液,油相分散体,浆糊,粉剂,散播的材料或颗粒的形式,它们通过喷射,喷雾,撒粉,散播或灌注被使用。使用方式要根据使用的目的。在任何一种情况下,根据本发明应当保证混合物的分布尽可能地细小和均匀一致。
以熟知的方式制备配料,如通过添加溶剂和/或载体。通常将惰性添加剂如乳化剂或分散剂和配料混合。
适合的表面活性剂是芳族磺酸(例如木质磺酸,苯酚磺酸,萘磺酸以及二丁基萘磺酸),脂肪酸,烷基磺酸和烷基芳香基磺酸,烷基硫酸酯,月桂基醚硫酸酯和脂肪族醇硫酸酯的碱金属盐,碱土金属盐和铵盐,以及硫酸化十六醇盐,硫酸化十七醇盐,硫酸化十八醇盐或硫酸化脂肪醇乙二醇醚盐,磺化萘和其衍生物与甲醛的缩合物,萘和萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基苯酚醚,乙氧基化异辛基苯酚,乙氧基化辛基苯酚或乙氧基化壬基苯酚,烷基苯酚聚乙二醇醚或三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷基醇,脂肪醇-环氧乙烷缩合物,乙氧基化蓖麻油,聚氧亚乙基烷基醚或聚氧丙烯,聚乙二醇醚醋酸月桂酯,山梨糖醇酯,木质素亚硫酸酯废溶液或甲基纤维素。
散播和撒粉的粉末材料,可以通过化合物Ⅰ,Ⅱ,Ⅲ或化合物Ⅰ,Ⅱ,Ⅲ的混合物与一种固体载体混合或一起研磨制备。
颗粒(例如,涂层颗粒,浸渍颗粒或均相颗粒)一般通过将这种活性成份与一固体载体结合制备。
填料或固体载体是,例如,如硅胶,硅石,硅酸盐,滑石,高岭土,石灰石,石灰,白垩,红玄武土,黄土,泥土,白云石,硅藻土,硫酸钙,硫酸镁,氧化镁,粉状合成材料等矿石土和如硫酸铵,磷酸铵,硝酸铵,尿素等肥料,以及植物原料产品如谷物粉,树皮粉,木粉以及果壳粉,纤维素粉或其它固体载体。
配料中一般含0.1~95%重量,优选0.5~90%重量的化合物Ⅰ或Ⅱ的一种,或是化合物Ⅰ,Ⅱ和Ⅲ的混合物。采用90%~100%纯度的活性成份,优选95%~100%(根据核磁共振NMR和高效液相色谱HPLC)。
通过将有害真菌或未受真菌感染的植物,种子,土壤,区域,材料或空间用杀真菌有效量的混合物或分开使用情况下的化合物Ⅰ,Ⅱ和Ⅲ处理,使用化合物Ⅰ,Ⅱ和Ⅲ或者其混合物或相应配料。在有害真菌感染之前或之后都可以使用。
在以下实验表现出化合物和混合物的杀菌作用:
活性成份,分开或一起,制备成在70%重量环己酮,20%重量NekanilLN(LutensolAP6,具有乳化和悬浮作用的湿剂,基于乙氧基化烷基苯酚)和10%重量EmulphorEL(EmulanEL,基于乙氧基化脂肪醇的乳化剂)中的20%的乳液以及用水稀释至所需的浓度。
通过测定被感染叶子面积以百分比进行评价。这些百分值将被转化成有效率。活性成份混合物的预计有效率根据Colby方程(R.S.Colby,Weeds15,20-22(1967))来确定,然后与观察的有效率进行比较。
Colby方程:
E=X+Y+Z-X·Y·Z/100
E当使用浓度为a和b的有效成份A和B的混合物时的预计有效率,以未处理的对照物的%表示,
X当使用浓度为a的活性成份A时的有效率,以未处理的对照物的%表示,
Y当使用浓度为b的活性成份B时的有效率,以未处理的对照物的%表示,
Z当使用浓度为c的活性成份C时的有效率,以未处理的对照物的%表示。
有效率为0意味着处理过的植物感染程度相当于未处理的对照植物;有效率为100意味着处理过的植物未经感染。
实施例1至12
防止小麦粉化霉菌的有效率
在盆中栽培的品种为”Frühgold”的小麦育苗的叶子上喷射水溶液喷剂至滴湿,喷剂由10%活性成份,63%环己酮和27%乳化剂组成。在喷射表面层干燥之后24小时,将小麦粉化霉菌的孢子(Erysiphegraminis var tritici)撒在育苗的叶子上。接着将测试的植物放入温室中,温室温度为20~22℃,空气相对湿度为75~80%。7天后目测霉菌的感染程度作为整个叶子面积的病变百分比。
病变叶子面积的百分比目测数据作为未处理对照物的百分比被转化为有效率。
有效率为0是未处理对照物的同种病变的程度,有效率为100是病变程度为0%。活性成份混合物的预计有效率用Colby方程测定(Colby,S.R.计算除草混合物的协同反应和对立反应,Weeds,15,P20-22,1967),并与所观察的有效率进行比较。
实施例 | 活性成份或混合物 | 在喷剂中活性成份的浓度(PPm) | 未处理对照物的有效率,% |
1V | 对照物(未处理) | (95%感染率) | 0 |
2V | Ⅰ | 10.250.06 | 9500 |
3V | Ⅱ | 10.250.06 | 84341 |
4V | Ⅲ | 0.250.06 | 341 |
5V | Ⅰ+Ⅱ1∶1 | 1+1 | 89 |
6V | Ⅰ+Ⅲ1∶1 | 0.25+0.25 | 45 |
7V | Ⅱ+Ⅲ1∶1 | 0.25+0.25 | 84 |
实施例 | 喷剂中活性成份的浓度 | 所观察的有效率 | 计算得到的有效率* |
8 | (Ⅰ+Ⅱ) 1+1Ⅲ 0.06 | 97 | 89 |
9 | (Ⅰ+Ⅲ) 0.25+0.25Ⅱ 0.06 | 78 | 46 |
10 | (Ⅰ+Ⅲ) 0.25+0.25Ⅱ 0.25 | 89 | 64 |
11 | Ⅰ 0.06(Ⅱ+Ⅲ) 0.25+0.25 | 92 | 84 |
12 | Ⅰ 0.25(Ⅱ+Ⅲ) 0.25 | 90 | 84 |
*根据Colby方程。
测试结果显示所有混合比例下所观察的有效率都要大于根据Colby方程计算的预计有效率。
Claims (15)
1.一种杀菌混合物,其中它包括协同作用量的一种化学式为Ⅰ的肟醚羧酸酯和一种化学式为Ⅱ的肟醚羧酸酰胺以及还有一种化学式为Ⅲ的吡咯,
2.权利要求1的杀菌混合物,其中化合物Ⅰ和化合物Ⅱ的重量比为1∶0.1至1∶10。
3.权利要求1的杀菌混合物,其中化合物Ⅰ和化合物Ⅲ的重量比为1∶0.1至1∶10。
4.权利要求1的杀菌混合物,其中化合物Ⅰ对化合物Ⅱ对化合物Ⅲ的重量比为1∶10∶1,10∶1∶1至1∶1∶10。
5.权利要求1的杀菌混合物,其中它配制成两部分,一部分由活性成份Ⅰ和/或Ⅲ在一种固体或液体载体中组成,另一部分由活性成份Ⅱ在一种固体或液体载体中组成。
6.权利要求1的杀菌混合物,其中它配制成两部分,一部分由活性成份Ⅰ和/或Ⅱ在一种固体或液体载体中组成,另一部分由活性成份Ⅲ在一种固体或液体载体中组成。
7.权利要求1的杀菌混合物,其中它配制成三部分,一部分由活性成份Ⅰ在一种固体或液体载体中组成,另一部分由活性成份Ⅱ在一种固体或液体载体中组成,第三部分由活性成份Ⅲ在一种固体或液体载体中组成。
8.控制有害真菌的方法,其中它包括用权利要求1中化学式为Ⅰ的化合物,权利要求1中化学式为Ⅱ的化合物,权利要求1中化学式为Ⅲ的化合物处理有害真菌,它们的生存环境,或未受有害真菌感染的植物,种子,土壤,区域,材料或空间。
9.权利要求8的方法,其中权利要求1的化合物Ⅰ和权利要求1的化合物Ⅱ以及权利要求1的化合物Ⅲ被同时一起或分开,或连续地使用。
10.权利要求8的方法,其中用权利要求1中的化合物Ⅰ以0.001~1.0kg/ha的量处理有害真菌,它们的生存环境,或未受有害真菌感染的植物,种子,土壤,区域,材料或空间。
11.权利要求8的方法,其中用权利要求1中的化合物Ⅱ以0.001~1.0kg/ha的量处理有害真菌,它们的生存环境,或未受有害真菌感染的植物,种子,土壤,区域,材料或空间。
12.权利要求8的方法,其中用权利要求1中的化合物Ⅲ以0.001~1.0kg/ha的量处理有害真菌,它们的生存环境,或未受有害真菌感染的植物,种子,土壤,区域,材料或空间。
13.权利要求1中的化合物Ⅰ在制备权利要求1的杀菌活性协同作用的混合物中的用途。
14.权利要求1中的化合物Ⅱ在制备权利要求1的杀菌活性协同作用的混合物中的用途。
15.权利要求1中的化合物Ⅲ在制备权利要求1的杀菌活性协同作用的混合物中的用途。
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